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Coastal marine atmospheric fog has recently been implicated as a potential source of ocean-derived monomethylmercury (MMHg) to coastal terrestrial ecosystems through the process of sea-to-land advection of foggy air masses followed by wet deposition. This study examined whether pumas (Puma concolor) in coastal central California, USA, and their associated food web, have elevated concentrations of MMHg, which could be indicative of their habitat being in a region that is regularly inundated with marine fog. We found that adult puma fur and fur-normalized whiskers in our marine fog-influenced study region had a mean (±SE) total Hg (THg) (a convenient surrogate for MMHg) concentration of 1544 ± 151 ng g -1 (N = 94), which was three times higher (P < 0.01) than mean THg in comparable samples from inland areas of California (492 ± 119 ng g -1 , N = 18). Pumas in California eat primarily black-tailed and/or mule deer (Odocoileus hemionus), and THg in deer fur from the two regions was also significantly different (coastal 28.1 ± 2.9, N = 55, vs. inland 15.5 ± 1.5 ng g -1 , N = 40). We suggest that atmospheric deposition of MMHg through fog may be contributing to this pattern, as we also observed significantly higher MMHg concentrations in lace lichen (Ramalina menziesii), a deer food and a bioindicator of atmospheric deposition, at sites with the highest fog frequencies. At these ocean-facing sites, deer samples had significantly higher THg concentrations compared to those from more inland bay-facing sites. Our results suggest that fog-borne MMHg, while likely a small fraction of Hg in all atmospheric deposition, may contribute, disproportionately, to the bioaccumulation of Hg to levels that approach toxicological thresholds in at least one apex predator. As global mercury levels increase, coastal food webs may be at risk to the toxicological effects of increased methylmercury burdens.

Opposing hypotheses posit that increasing primary productivity should result in either greater or lesser contaminant accumulation in stream food webs. We conducted an experiment to evaluate primary productivity effects on MeHg accumulation in stream consumers. We varied light for 16 artificial streams creating a productivity gradient (oxygen production =0.048-0.71 mg O2 L(-1) d(-1)) among streams. Two-level food webs were established consisting of phytoplankton/filter feeding clam, periphyton/grazing snail, and leaves/shredding amphipod (Hyalella azteca). Phytoplankton and periphyton biomass, along with MeHg removal from the water column, increased significantly with productivity, but MeHg concentrations in these primary producers declined. Methylmercury concentrations in clams and snails also declined with productivity, and consumer concentrations were strongly correlated with MeHg concentrations in primary producers. Heterotroph biomass on leaves, MeHg in leaves, and MeHg in Hyalella were unrelated to stream productivity. Our results support the hypothesis that contaminant bioaccumulation declines with stream primary production via the mechanism of bloom dilution (MeHg burden per cell decreases in algal blooms), extending patterns of contaminant accumulation documented in lakes to lotic systems.

Methylmercury (MeHg) is a contaminant of global concern that bioaccumulates and bioamagnifies in marine food webs. Lower trophic level fauna are important conduits of MeHg from sediment and water to estuarine and coastal fish harvested for human consumption. However, the sources and pathways of MeHg to these coastal fisheries are poorly known particularly the potential for transfer of MeHg from the sediment to biotic compartments. Across a broad gradient of human land impacts, we analyzed MeHg concentrations in food webs at ten estuarine sites in the Northeast US (from the Hackensack Meadowlands, NJ to the Gulf of Maine). MeHg concentrations in water column particulate material, but not in sediments, were predictive of MeHg concentrations in fish (killifish and Atlantic silversides). Moreover, MeHg concentrations were higher in pelagic fauna than in benthic-feeding fauna suggesting that MeHg delivery to the water column from methylation sites from within or outside of the estuary may be an important driver of MeHg bioaccumulation in estuarine pelagic food webs. In contrast, bulk sediment MeHg concentrations were only predictive of concentrations of MeHg in the infaunal worms. Our results across a broad gradient of sites demonstrate that the pathways of MeHg to lower trophic level estuarine organisms are distinctly different between benthic deposit feeders and forage fish. Thus, even in systems with contaminated sediments, transfer of MeHg into estuarine food webs maybe driven more by the efficiency of processes that determine MeHg input and bioavailability in the water column.

We investigated the dietary pathways of mercury transfer in the food web of Morency Lake (Canada) to determine the influence of carbon source and habitat use on mercury bioaccumulation in fish. Whole-body concentrations of methylmercury (MeHg) were significantly different in four fish species (white sucker, brown bullhead, pumpkinseed and smallmouth bass) and increased with both trophic position and greater feeding on offshore (versus littoral) carbon. An examination of fish gut contents and the depth distribution of invertebrates in Morency Lake showed that smallmouth bass and brown bullhead were supplementing their littoral diet with the consumption of either opossum shrimp (Mysis diluviana) or profundal amphipods in offshore waters. The zooplanktivore Mysis had significantly higher MeHg concentrations than zooplankton and benthic invertebrates, and it was an elevated source of MeHg to smallmouth bass. In contrast, profundal amphipods consumed by brown bullhead did not have higher MeHg concentrations than littoral amphipods. Instead, partitioning of benthic invertebrate resources likely explains the greater MeHg bioaccumulation in brown bullhead, associated with offshore feeding of amphipods. White sucker and brown bullhead had a similar trophic position but white sucker consumed more chironomids, which had one-third the MeHg concentration of amphipods. Our findings suggest that offshore feeding in a lake can affect fish MeHg bioaccumulation via two different processes: (1) the consumption of MeHg-enriched pelagic prey, or (2) resource partitioning of benthic primary consumers with different MeHg concentrations. These observations on the mechanisms of habitat-specific bioaccumulation highlight the complexity of MeHg transfer through lake food webs.

Top-level piscivores are highly sought after for consumption in freshwater fisheries, yet these species contain the highest levels of the neurotoxin monomethylmercury (MMHg) and therefore present the greatest concern for MMHg exposure to humans. The slow elimination of MMHg is one factor that contributes to high levels of this contaminant in fish; however, little quantitative information exists on elimination rates by top predators in nature. We determined rates of MMHg elimination in northern pike (Esox lucius) by transferring fish that had naturally accumulated isotope-enriched MMHg (spike MMHg) through a whole-lake Hg loading study to a different lake. Over a period of ~7 y, pike were periodically recaptured and a small amount of muscle tissue was extracted using a nonlethal biopsy. Spike total mercury (THg) persisted in muscle tissue throughout the entire study despite discontinuing exposure upon transfer to the new lake. Spike THg burdens increased for the first ~460 d, followed by a decline to 65% of original burden levels over the next 200 d, and subsequently reached a plateau near original burden levels for the remainder of the study. We estimated the half-life of muscle THg to be 3.3 y (1193 d), roughly 1.2- to 2.7-fold slower than predicted by current elimination models. We advocate for further long-term field studies that examine kinetics of MMHg in fish to better inform predictive models estimating the recovery of MMHg-contaminated fisheries.

Based on a laboratory experiment, we estimated the net trophic transfer efficiency of methylmercury to lake trout Salvelinus namaycush from its prey to be equal to 76.6 %. Under the assumption that gross trophic transfer efficiency of methylmercury to lake trout from its prey was equal to 80 %, we estimated that the rate at which lake trout eliminated methylmercury was 0.000244 day(-1). Our laboratory estimate of methylmercury elimination rate was 5.5 times lower than the value predicted by a published regression equation developed from estimates of methylmercury elimination rates for fish available from the literature. Thus, our results, in conjunction with other recent findings, suggested that methylmercury elimination rates for fish have been overestimated in previous studies. In addition, based on our laboratory experiment, we estimated that the net trophic transfer efficiency of inorganic mercury to lake trout from its prey was 63.5 %. The lower net trophic transfer efficiency for inorganic mercury compared with that for methylmercury was partly attributable to the greater elimination rate for inorganic mercury. We also found that the efficiency with which lake trout retained either methylmercury or inorganic mercury from their food did not appear to be significantly affected by the degree of their swimming activity.

While mercury is a health hazard to humans and wildlife, the biogeochemical processes responsible for its bioaccumulation in pelagic food webs are still being examined. Previous studies have indicated both "bottom-up" control of piscivorous fish Hg content through methylmercury.(MeHg) supply, as well as site-specific trophic factors. We evaluated ten studies from the western Great Lakes region to examine the similarity of MeHg trophic transfer efficiency within the pelagic food web, and assessed regional-scale spatial variability. Analyses of bioaccumulation and biomagnification factors between water, seston, zooplankton, and preyfish indicated that the largest increases in MeHg occurred at the base of the food web, and that the relative extent of trophic transfer was similar between sites. Positive correlations were observed between aqueous unfiltered MeHg, total Hg, and dissolved organic carbon, and measures of the efficiency of MeHg trophic transfer were consistent across widely disparate systems (both natural and experimentally manipulated) throughout North America. Such similarity suggests that the aqueous supply of MeHg is largely controlling bioaccumulation in pelagic food webs, while local, lake-specific variability can result from an array of trophic (biological) factors.

Stream ecosystems are widely contaminated by mercury (Hg) via atmospheric transport and deposition in watersheds. Dissolved organic carbon (DOC) is well-known to be the dominant ligand for aqueous methylmercury (MeHg), the bioaccumulative form of Hg in aquatic food webs. However, it is less clear if and how the concentration and character (e.g., aromaticity) of DOC influences the availability of dissolved MeHg to stream food webs. In this work, we analyzed total-Hg and/or MeHg concentrations in water, seston, and macroinvertebrates (filter-feeding hydropsychid caddisflies), and other physiochemical properties in 30 streams along a south-north geographic gradient in eastern Minnesota that corresponds to substantial changes in dominant land cover (i.e., agriculture, urban, wetland, and forest). In general, MeHg concentrations in seston and hydropsychids were higher in watersheds with more forest and wetland coverage, and increased with dissolved MeHg concentration. However, we found that the efficiency of MeHg incorporation into the stream food webs (i.e., bioconcentration factors of MeHg in both seston and hydropsychids, BCF(MeHg) = solid MeHg ÷ dissolved MeHg) decreased significantly with DOC concentration and aromaticity, suggesting that MeHg bioavailability to the base of food webs was attenuated at higher levels of terrestrial DOC. Therefore, our findings suggest that there is a dual role of DOC on MeHg cycling in streams: terrestrial DOC acts as the primary carrier ligand of dissolved MeHg for transport into surface waters, yet this aromatic DOC also attenuates dissolved MeHg uptake by aquatic food webs. Thus, consideration of MeHg bioavailability and its environmental regulation could help improve predictive models of MeHg bioaccumulation in stream ecosystems.

Different behaviors of inorganic mercury [Hg(II)] and methylmercury (MeHg) during trophic transfer along the marine food chain have been widely reported, but the mechanisms are not fully understood. The bioavailability of ingested mercury, quantified by assimilation efficiency (AE), was investigated in a marine fish, the grunt Terapon jarbua, based on mercury subcellular partitioning in prey and purified subcellular fractions of prey tissues. The subcellular distribution of Hg(II) differed substantially among prey types, with cellular debris being a major (49-57% in bivalves) or secondary (14-19% in other prey) binding pool. However, MeHg distribution varied little among prey types, with most MeHg (43-79%) in heat-stable protein (HSP) fraction. The greater AEs measured for MeHg (90-94%) than for Hg(II) (23-43%) confirmed the findings of previous studies. Bioavailability of each purified subcellular fraction rather than the proposed trophically available metal (TAM) fraction could better elucidate mercury assimilation difference. Hg(II) associated with insoluble fraction (e.g. cellular debris) was less bioavailable than that in soluble fraction (e.g. HSP). However, subcellular distribution was shown to be less important for MeHg, with each fraction having comparable MeHg bioavailability. Subcellular distribution in prey should be an important consideration in mercury trophic transfer studies., (2010 Elsevier B.V. All rights reserved.)

Concentrations and biomagnification of total mercury (TotHg) and methyl mercury (MeHg) were studied in selected species from the pelagic food web in Kongsfjorden, Svalbard. Twelve species of zooplankton, fish and seabirds, were sampled representing a gradient of trophic positions in the Svalbard marine food web. TotHg and MeHg were analysed in liver, muscle and/or whole specimens. The present study is the first to provide MeHg levels in seabirds from the Svalbard area. The relative MeHg levels decreased with increasing levels of TotHg in seabird tissues. Stable isotopes of nitrogen (delta(15)N) were used to determine the trophic levels and the rate of biomagnification of mercury in the food web. A linear relationship between mercury levels and trophic position was found for all seabird species combined and their trophic level, but there was no relationship within species. Biomagnification factors were all >1 for both TotHg and MeHg, indicating biomagnification from prey to predator. TotHg levels in the different seabirds were similar to levels detected in the Kongsfjorden area in the 1990s.

We examined the transfer of Cd, methylmercury (MeHg), and Po in an estuarine food chain (from phytoplankton to zooplankton [Daphnia pulex] to killifish [Fundulus heteroclitus] and, finally, to juvenile striped bass [Morone saxatilis]) to better understand both the extent to which these elements may biomagnify and the underlying mechanisms governing this biomagnification. Among the phytoplankton examined (Cyclotella meneghiniana and Chlamdomonas reinhardtii), metal uptake was rapid, and volume concentration factors for all metals reached values between 10(4) and 10(5). The resulting assimilation efficiencies (AEs) of ingested metals in all animals were highest for MeHg, with values greater than 76%. The AEs of Cd were 21 to 33% in D. pulex, 1 to 16% in F. heteroclitus, and 38 to 56% in M. saxatilis. Polonium AEs were 69 to 87% in D. pulex, 25 to 41% in F. heteroclitus, and 9 to 21% in M. saxatilis. Loss rate constants (ke) of metals in D. pulex ranged from 0.04/d for MeHg to 0.39/d for Po; metal ke values for F. heteroclitus ranged from 0.01 to 0.02/d. Using a kinetic model, we showed that the trophic transfer factor, defined as the ratio of metal concentration in predatory animals to metal concentration in prey organisms, was greater than unity for all three metals in D. pulex feeding on phytoplankton, suggesting that these metals may be biomagnified at this trophic step. In killifish feeding on D. pulex, the trophic transfer factor was consistently greater than one for MeHg, consistently less than one for Cd, and from 0.1 to 1.4 for Po, suggesting that both MeHg and Po have the potential to biomagnify at this trophic step.

Bioaccumulation potential in aquatic biota is typically expressed using ratios of chemical concentrations in organism tissue (typically whole body) relative to chemical exposure concentrations, such as bioconcentration factors (BCFs). Past reviews of metal BCFs for aquatic biota, which account for water-only exposures, have shown that BCFs are often highly variable between organisms and generally inversely related to exposure concentration. This paper further evaluates trends in metal bioaccumulation data by evaluating data for bioaccumulation factors (BAFs) and trophic transfer factors (TTFs). Bioaccumulation factor data were compiled from field studies that account for combined waterborne and dietary metal exposures. Trophic transfer factor data for metals were compiled from laboratory studies in which aquatic food chains were simulated. Natural aquatic food webs are rarely sufficiently understood to properly evaluate exact predator-prey relationships (i.e., TTFs). Results indicate that field BAFs, like laboratory BCFs, tend to be significantly (p < or = 0.05) inversely related to exposure concentration. Bioaccumulation factors are frequently 100-1000 times larger than BCFs for the same metal and species. This difference is attributed to both lower exposure levels in the field and inclusion of the dietary exposure route. Trophic transfer factors for the metals reviewed, including selenium and methyl mercury were also observed to be inversely related to exposure concentration, particularly at lower exposure concentrations. These inverse relationships have important implications for environmental regulations (e.g., hazard classification and tissue residue-based water quality criteria) and for the use of metal bioaccumulation data in site-specific environmental evaluations, such as ecological and human health risk assessments. Data presented indicate that for metals and metalloids, unlike organic substances, no one BAF or TTF can be used to express bioaccumulation and/or trophic transfer without consideration of the exposure concentration.

Humans are exposed to methylmercury (MeHg) principally by consumption of marine fish. The coastal zone supports the majority of marine fish production, and may therefore be an important source of MeHg to humans; however, little is known about the bioaccumulation of MeHg in near-shore marine ecosystems. We examined MeHg in microseston, zooplankton, a decapod crustacean, and four representative species of finfish that differ in trophic status and/or prey selection in Long Island Sound (LIS), a large coastal embayment in the northeastern United States. MeHg biomagnifies in LIS; levels in microseston were 10(4.2) greater than those in water and 2.3-fold less than zooplankton. MeHg concentrations were related positively to fish length for each species, but often varied considerably among larger individuals. This may be due to differences in the past dietary MeHg exposure of these fish, some of which are migratory. Sedimentary production and mobilization can account for most of the MeHg in microseston of LIS, and by extension, other near-shore locations. Hence, much of the MeHg in higher trophic levels of coastal marine ecosystems, including fishes destined for human consumption, may be attributed to net sedimentary production and dietary bioaccumulation.

We modeled the flow of methyl mercury, a toxic global pollutant, in the Faroe Islands marine ecosystem and compared average human methyl mercury exposure from consumption of pilot whale meat and fish (cod, Gadus morhua) with current tolerable weekly intake (TWI) levels. Under present conditions and climate change scenarios, methyl mercury increased in the ecosystem, translating into increased human exposure over time. However, we saw greater changes as a result of changing fishing mortalities. A large portion of the general human population exceed the TWI levels set by the World Health Organization [WHO; 1.6 microg/kg body weight (bw)], and they all exceed the reference dose (RfD) of 0.1 microg/kg bw/day set by the U.S. Environmental Protection Agency (EPA; equivalent to a TWI of 0.7 microg/kg bw). As a result of an independent study documenting that Faroese children exposed prenatally to methyl mercury had reduced cognitive abilities, pregnant women have decreased their intake of whale meat and were below the TWI levels set by the WHO and the U.S. EPA. Cod had approximately 95% lower methyl mercury concentrations than did pilot whale. Thus, the high and harmful levels of methyl mercury in the diet of Faroe Islanders are driven by whale meat consumption, and the increasing impact of climate change is likely to exacerbate this situation. Significantly, base inflow rates of mercury into the environment would need to be reduced by approximately 50% to ensure levels of intake below the WHO TWI levels, given current levels of whale consumption.

We studied the effect of zooplankton diet on MeHg accumulation in different zooplankton size-fractions from lakes of different trophic status. Using fatty acid biomarkers, we tested the hypotheses that (a) variations of MeHg concentrations are determined bythe taxonomic composition of zooplankton and (b) concentrations of dietary algal and bacterial compounds can predict MeHg concentrations of seston (10-64 microm), micro- (100-200 microm), meso- (200-500 microm), and macrozooplankton (>500 microm) in lakes on Vancouver Island, Canada. MeHg concentrations increased from seston (4-48 ng g dry weight(-1)) to macrozooplankton (94-240 ng g dry weight(-1)), indicating that MeHg accumulated as a function of plankton size. Results from linear regression analysis showed that MeHg concentrations were not significantly related to the taxonomic composition of zooplankton. However, using dietary lipid biomarkers, we demonstrated that bacterial diet (R2 = 0.50; p < 0.01) could better predict variations of MeHg concentrations in zooplankton than essential algal diet (R2 = 0.35; p < 0.01). Because MeHg accumulation within the planktonic food web was higher (20x) than the observed accumulation of total bacterial (6.5x) and algal (4.7x) diet biomarkers, zooplankton retained dietary MeHg more efficiently than bacterial and algal diet compounds. These results indicate that MeHg of macrozooplankton, the preferred prey size of planktivorous fish, is more efficiently transferred than essential diet compounds to organisms at higher trophic levels.

Total Hg and MMHg concentrations were assessed in more than 350 fish and shellfish samples. Hg concentrations in Greater North Sea fish of prey range from 0.039 mg kg(-1) wet weight (ww; for ray) to 0.61 mg kg(-1) ww (for dogfish) and for all other fish species, from 0.045 mg kg(-1) ww (for plaice) to 0.33 mg kg(-1) ww (for sand sole), with 95 +/- 2% of the Hg content in the MMHg form. In Belgian coastal zone, fish concentrations range from 0.063 mg kg(-1) ww for plaice to 0.13 mg kg(-1) ww for flounder, with 82-87% of the Hg content in the MMHg form. In fish of the Scheldt, which is a very polluted estuary, Hg levels, as well as the percent MMHg of the total Hg, were lower than in the two zones previously mentioned. The intraspecies variability is of the order of 50% in each of the three zones. In liver tissue, a much larger variability was observed than in muscle tissue, except for fish species of the Scheldt. In most cases, the MMHg fraction in a particular fish species is inversely related to the intraspecies variability. Bioconcentration and biomagnification factors (BCF and BMF, respectively) were assessed. MMHg-BMFs were a few orders of magnitude higher than Hg(inorganic)-BMFs, and for the same species were always highest in the Greater North Sea and lowest in the Scheldt. For each of the Belgian coastal zone four species, a weak positive correlation between Hg content and fish length was found; however, the larger the size-range, the better the correlation. Taking fish length into account, a statistically significant difference in contamination level was observed for species sampled from the different geographical zones.

In the Willamette River Basin (WRB, Oregon, USA), health advisories currently limit consumption of fish that have accumulated methylmercury (MeHg) to levels posing a potential health risk for humans. Under the Clean Water Act, these advisories create the requirement for a total maximum daily load (TMDL) for mercury in the WRB. A TMDL is a calculation of the maximum amount of a pollutant that a body of water can receive and still meet water-quality standards. Because MeHg is known to biomagnify in aquatic food webs, a basin-specific biomagnification factor can be used, given a protective fish tissue criterion, to estimate total mercury concentrations in surface waters required to lower advisory mercury concentrations currently in fish in the WRB. This paper presents an aquatic food web biomagnification model that simulates inorganic mercury (Hg(II)) and MeHg accumulation in fish tissue and estimates WRB-specific biomagnification factors for resident fish species of concern to stakeholders. Probabilistic (two-dimensional Monte Carlo) techniques propagate parameter variability and uncertainty throughout the model, providing decision makers with credible range information and increased flexibility in establishing a specific mercury target level. The model predicts the probability of tissue mercury concentrations in eight fish species within the range of concentrations measured in these species over 20 years of water-quality monitoring. Estimated mean biomagnification factor values range from 1.12 x 10(6) to 7.66 x 10(6) and are within the range of U.S. Environmental Protection Agency national values. Several WRB-specific mercury target levels are generated, which very by their probability of affording human health protection relative to the federal MeHg tissue criterion of 0.30 mg/kg. Establishing a specific numeric target level is, however, a public policy decision, and one that will require further discussions among WRB stakeholders.

Mercury is a unique element that, unlike many metals, has no essential biological function. It is liquid at room temperature and is 13.6 times heavier than water. Its unique physical properties have been exploited for a variety of uses such as in mercury switches, thermostats, thermometers, and other instruments. Its ability to amalgamate with gold and silver are used in mining these precious metals and as a dental restorative. Its toxic properties have been exploited for medications, preservatives, antiseptics, and pesticides. For these reasons there have been many industrial uses of mercury, and occupational exposures of workers and industrial emissions and effluents contaminating air, water, soil, and ultimately food chains have long been a matter of great public health concern. This paper examines briefly six cases representing various forms of exposure to different species of mercury, and indicates the methodological issues in estimating exposure, bioavailability and absorption; these cases include Minamata disease in Japan, organic mercury poisoning in Iraq, methylmercury (MeHg) exposure in the Amazon, dimethylmercury (PMM) in the laboratory, an elemental mercury spill in Cajamarca, Peru, and a mercury-contaminated building in Hoboken, NJ, USA. Other scenarios that are not described include occupational exposure to mercury salts, mercurial preservatives in vaccines, cultural and ritualistic uses of mercury, and mercury in dental amalgams.

The influence of the Nyanza Chemical Waste Dump Superfund Site on the Sudbury River, Massachusetts, was assessed by analysis of sediment, fish prey organisms, and predator fish from four locations in the river system. Whitehall Reservoir is an impoundment upstream of the site, and Reservoir #2 is an impoundment downstream of the site. Cedar Street is a flowing reach upstream of the site, and Sherman Bridge is a flowing reach downstream of the site. Collections of material for analysis were made three times, in May, July, and October. Sediment was analyzed for acid-volatile sulfide (AVS), simultaneously-extracted (SEM) metals (As, Cd, Cr, Hg, Pb, Sb, Zn), and total recoverable Hg. The dominant predatory fish species collected at all sites, largemouth bass (Micropterus salmoides), was analyzed for the same suite of metals as sediment. Analysis of stomach contents of bass identified small fish (yellow perch Perca flavescens, bluegill Lepomis macrochirus, and pumpkinseed Lepomis gibbosus), crayfish, and dragonfly larvae as the dominant prey organisms. Samples of the prey were collected from the same locations and at the same times as predator fish, and were analyzed for total and methyl mercury. Results of AVS and SEM analyses indicated that sediments were not toxic to aquatic invertebrates at any site. The SEM concentrations of As, Cd, and Cr were significantly higher at Reservoir #2 than at the reference sites, and SEM As and Cd were significantly higher at Sherman Bridge than at Cedar St. Sediment total Hg was elevated only at Reservoir #2. Hg was higher at site-influenced locations in all fish species except brown bullhead (Ameiurus nebulosus). Cd was higher in bluegill, black crappie (Pomoxis nigromaculatus), and brown bullhead, and Cr was higher in largemouth bass fillet samples but not in whole-body samples. There were no seasonal differences in sediment or prey organism metals, but some metals in some fish species did vary over time in an inconsistent manner. Predator fish Hg concentration was significantly linearly related to weighted prey organism methyl Hg concentration. Largemouth bass Hg was significantly lower at Reservoir #2 in our study than in previous investigations in 1989 and 1990. High concentrations of inorganic Hg remain in river sediment as a result of operation of the Nyanza site, and fish Hg concentrations in river reaches downstream of the site are elevated compared to upstream reference sites. However, the differences are relatively small and Hg concentrations in largemouth bass from the site-influenced locations are no higher than those from some other, nearby uncontaminated sites. We hypothesize that this results from burial of contaminated sediment with cleaner material, which reduces bioavailability of contaminants and possibly reduces methylation of mercury.

We developed an integrated food web model for mercury, using the CATS (Contaminants in Aquatic and Terrestrial ecoSytems) model developed by Traas and co-workers (Traas, T.P.; Stäb, J.A.; Kramer, P.R.G.; Cofino, W.P.; Aldenberg, T. Modeling and risk assessment of tributyltin accumulation in the food web of a shallow freshwater lake. Environ. Sci. Technol. 1996, 30 (4), 1227-1237). It was translated into the MatLab mathematical programming language and been adapted for the modeling of mercury. Mercury CATS now models four species of mercury (unreactive mercury, zero valent mercury, divalent mercury, and methylmercury) and their environmental and interactions using the mercury speciation kinetics model article by Bale (Bale, A.E. Modeling aquatic mercury fate in Clear Lake, Calif. J. Env. Eng. 2000, 126 (2), 153-163.) as a guideline. The mercury cycling kinetics include methylation of divalent mercury, photo-oxidation of zero valent mercury, reduction of divalent mercury, adsorption and desorption of divalent and methylmercury, volatilization of zero valent mercury, and uptake into the food web. A lake food web consisting of phytoplankton, rooted vegetation, zooplankton, crayfish, freshwater clams, amphipods, chironomids, eels, killifish, bass, and ospreys traces growth of the various compartments, uptake of both divalent and methylmercury, and the movement of both divalent and methylmercury through the food web via feeding relationships. This model design is sufficiently flexible that the incorporation of new scientific information can be easily done as our understanding of both the organisms and mercury's environmental chemistry increases.

Total mercury (THg) and methylmercury (MeHg) levels have been determined in fish species representing various tropic levels in four major hydroelectric reservoirs (Mtera, Kidatu, Hale-Pangani, Nyumba ya Mungu) located in two distinct geographical areas in Tanzania. The Mtera and Kidatu reservoirs are located along the Great Ruaha River drainage basin in the southern central part of the country while the other reservoirs are located within the Pangani River basin in the north eastern part of Tanzania. Fish mercury levels ranged from 5 to 143 microg/kg (mean 40 microg/kg wet weight) in the Mtera Reservoir, and from 7 to 119 microg/kg (mean 21 microg/kg) in the Kidatu Reservoir downstream of the Great Ruaha River. The lowest THg levels, in the range 1-10 microg/kg (mean 5 microg/kg), were found in fish from the Nyumba ya Mungu (NyM) Reservoir, which is one of the oldest reservoirs in the country. Fish mercury levels in the Pangani and Hale mini-reservoirs, downstream of the NyM Reservoir, were in the order of 3-263 microg/kg, with an average level of 21 microg/kg. These THg levels are among the lowest to be reported in freshwater fish from hydroelectric reservoirs. Approximately 56-100% of the total mercury in the fish was methylmercury. Herbivorous fish species contained lower THg levels than the piscivorous species; this was consistent with similar findings in other fish studies. In general the fish from the Tanzanian reservoirs contained very low mercury concentrations, and differed markedly from fish in hydroelectric reservoirs of similar age in temperate and other regions, which are reported to contain elevated mercury concentrations. The low levels of mercury in the fish correlated with low background concentrations of THg in sediment and flooded soil (mean 2-8 microg/kg dry weight) in the reservoir surroundings. This suggested a relatively clean reservoir environment that has not been significantly impacted by mercury contamination from natural or anthropogenic sources.

We investigated factors causing mercury (Hg) concentrations in northern pike to exceed the consumption advisory level (>500 ng/g) in some inland lakes of Isle Royale National Park. Using Hg-clean techniques, we collected water, zooplankton, macro invertebrates, and fishes in 1998 and 1999 from one advisory lake, Sargent Lake, for analysis of total mercury (Hg(T)) and methylmercury (MeHg). For comparison, samples were also collected from a non-advisory lake, Lake Richie. Concentrations of Hg(T) in northern pike were significantly higher in Sargent Lake (P<0.01). Counter to expectations, mean concentrations of both Hg(T) and MeHg in open water samples were slightly higher in Lake Richie. However, zooplankton in Sargent Lake contained higher average concentrations of Hg(T) and MeHg than in Lake Richie. Mercury concentrations in macro invertebrates were similar between lakes, but different between taxa. The two lakes exhibited similar Hg(T) concentrations in age-1 yellow perch and adult perch but concentrations in large adult perch (>160 mm) in Sargent Lake were twice the concentrations in Lake Richie. Analysis of stable isotopes (delta(13)C and delta(15)N) in biota showed that pike from the two lakes are positioned at the same trophic level (4.2 and 4.3), but that the food web is more pelagic-based in Sargent and benthic-based in Richie. Factors causing concentrations in large pike to be higher in Sargent Lake may include higher bioavailability of methylmercury and a food web that enhances bioaccumulation.

When exposed to methylmercury in the laboratory, grass shrimp, Palaemonetes pugio, parasitized by the isopod Probopyrus pandalicola, accumulated lower concentrations of mercury than their unparasitized counterparts. The parasitic isopod accumulated far less mercury than the grass shrimp. When exposed to mercury in a contaminated field site, mummichogs, Fundulus heteroclitus, parasitized with the nematode Eustrongylides, similarly accumulated lower concentrations of mercury than unparasitized fish, and the parasite similarly accumulated less than the host. The lower uptake by the parasites compared to their hosts is counter to the general view of biomagnification of methylmercury, since parasites are a trophic level above their hosts. The mechanism whereby parasitized animals accumulate less toxicant than unparasitized ones is unknown, but may be partially due to lower metabolic rate.

A comparative analysis of inorganic mercury (Hg(II)) and methylmercury (MMHg) bioaccumulation by the herbivorous fish Ctenopharyngodon idella, via the direct and "direct+trophic" routes, was investigated experimentally. The direct contamination was based on fairly low exposure conditions (Hg(II), 300 ng small middle dotL(-1); MMHg, 30 ng small middle dotL(-1)), for 15 and 30 days. The trophic uptake was based on ingestion of macrophyte leaves (Elodea densa), previously exposed for 87 days to similar Hg concentrations. Results revealed high capacities of bioaccumulation in fish via the direct route, with accumulation factors of 1000 for Hg(II) and 13,000 for MMHg. Hg concentrations measured after direct+trophic contamination were very much greater than those measured after direct exposure, owing to considerable metal burdens accumulated in plants and to large biomasses ingested. Nevertheless, estimated trophic transfer rates were fairly low: 2% for Hg(II) and 13% for MMHg. MMHg determinations in elodea leaves and fish muscle samples reveal significant methylation and demethylation reactions., (Copyright 2001 Academic Press.)

Applying the classic geochemical technique of stable carbon isotope ratios (delta13C), we confirmed the existence of a trophic link between fine particulate matter (FPM) and zooplankton in freshwater ecosystems, and examined possible reasons for the elevated MeHg concentrations ([MeHg]) in hydroelectric reservoirs as compared to natural lakes. Comparing natural and flooded environments, the delta13C and [MeHg] values for FPM and zooplankton differ significantly. Using a mixing model to calculate the contribution of terrestrial carbon to FPM, the differences in delta13C between natural and flooded sites are explained by an increasingly important autochthonous component in reservoirs. The stable isotopic evidence presented here strongly suggests that, despite the much greater abundance of detrital vascular-plant carbon, microalgae are important in supporting aquatic food webs in the oligotrophic flooded systems studied. Due to a significant inverse relationship between [MeHg] in FPM and the percentage of terrestrial carbon (r2 = 0.87), we propose that the higher [MeHg] in the zooplankton of flooded sites as compared to lakes are the result of proportionally higher levels of autochthonous material (algae/bacteria; i.e. potential sources/methylators of Hg) in the FPM of reservoirs.

Concentrations of mercury (Hg), methylmercury (MMHg), arsenic (As), selenium (Se), and cadmium (Cd) were measured in atmospheric deposition, stream water, and biota in two streams in western Maryland. Overall, concentrations were slightly higher in the water of the lower pH Herrington Creek tributary (HRCT). Bioaccumulation factors were also higher for HRCT compared to Blacklick Run (BLK). MMHg concentrations in biota increased with trophic level and essentially all the Hg was as MMHg in predatory insects and insectivorous/carnivorous fish. Thus, the overall trophic status of the organism was indicated by the %MMHg in its tissues. Levels of As, Se, Cd, and Hg, however, decreased with increasing trophic level. Adsorption of As to the exoskeleton of invertebrates appears to be an important accumulation mechanism. MMHg was distributed evenly throughout crayfish and fish organs, whereas As, Se, Cd, and Hg were found in higher concentrations in detoxifying organs. Concentrations in biota in this study were somewhat elevated compared to other rural sites, but were less than those of point source-contaminated sites. Overall, as atmospheric inputs to the two watersheds were similar, the results of this study show the importance of water chemistry in determining the bioaccumulation of the metals and metalloids into insects. Subsequent transfer to higher trophic levels is related to both the ability of the organisms to depurate and the mode of accumulation, either directly from water or from food.

Cadmium (Cd) and methylmercury (MeHg) trophic transfers were analyzed between the Asiatic clam Corbicula fluminea and the crayfish Astacus astacus. Metal bioaccumulation in crayfish was quantified after 5, 10, and 15 days of exposure via daily ingestion of soft bodies of C. fluminea, previously exposed during 7 days to Cd (20 microg. L(-1)) and MeHg (4 microg. L(-1)). Bioaccumulation kinetics in the predator were investigated at organ and tissue levels: hemolymph, tail muscle, hepatopancreas, gills, stomach/mesenteron, intestine, green gland, carapace. Trophic transfer rates were estimated at the whole organism level. Results showed marked differences (1) in assimilation efficiencies, mean transfer rates being 5% for Cd and 16% for MeHg; and (2) in the metal distribution within the different tissue compartments of the crayfish: for Cd, the trophic uptake leads to high concentrations in the hepatopancreas and small accumulation in the muscle tissue; for MeHg, the highest levels of bioaccumulation occur in the green gland and in the tail muscle. From an ecotoxicological point of view, these experimental data suggest a small risk of Cd transfer between the crayfish and predators, humans included; on the other hand, Hg distribution in the muscle and accumulation trends in this tissue represent an obvious risk of transfer.

Current paradigms regarding the bioaccumulation of mercury are rooted in observations that monomethyl mercury (meHg) biomagnifies along pelagic food chains. However, mechanisms regulating the formation of meHg, its initial incorporation at the base of pelagic food chains, and its subsequent trophic transfer remain controversial. Here we use field data from 15 northern Wisconsin lakes, equilibrium aqueous speciation modeling, and statistical modeling to revisit several hypotheses about the uptake, distribution, and fate of inorganic Hg (HgII) and meHg in aquatic biota. Our field data comprise determinations of total Hg (HgT) and meHg in surface waters, sediments, microseston, zooplankton, and small fish in each of the study lakes. For these lake waters, strong positive correlations between DOC and aqueous concentrations of mercury along with negative correlations between DOC and the seston-water partitioning of mercury indicate that organic ligands bind HgII and meHg strongly enough to dominate their apparent aqueous speciation. In the microseston, zooplankton and fish, meHg concentrations and bioaccumulation factors (BAFs) increased with increasing trophic level while biotic concentrations of HgII decreased--indicating that meHg was indeed the biomagnified species of mercury. For all trophic levels, meHg concentrations varied positively with the calculated aqueous concentration of meHg+ (free ion), especially when coupled with pH, or meHgOH (hydroxide) species but not with meHgCl0, the neutral chloride complex. These findings suggest that: (1) the passive uptake of meHg does not control bioaccumulation at the base of aquatic food webs in nature (i.e. phyto- and bacterioplankton); (2) correlation with pH and DOC largely reflect the supply and bioavailability of meHg to lower trophic levels; and (3) meHg concentrations at higher trophic levels reflect uptake at low trophic levels and other factors, such as diet and growth. Low concentrations of meHg in surficial sediments indicate that the fates of biotic HgII and meHg are different. Most biotic meHg is demethylated rather than buried in lake sediments.